Indigoid dyestuffs and process of making same



Patented Jan. 14, 1936 UNITED STATES INDIGOID DYESTUFFS AND PROCESS OF-MAKING SAME Ernst Sticklin, Binningen, near Basel, Switzerland, assignorto Society of Chemical Industry in Basie, Basel, Switzerland No Drawing.Application September 10,

Serial No. 743,487. 22, 1933 13 Claims.

This invention relates to the manufacture of new indigoid vat-dyestufisfrom hydroxythionaphthenes of the general formula ple,4,6-dimethyl--chloro-7-bromo-3 hydroxythionaphthene,4,6-dimethyl-5,7-dichloro-3-hydroxythionaphthene, 4,6-dimethyl 5bromo-lchloro 3 hydroxythionaphthene, 4,6-dimethyl-5,7-dibromo-3-hydroxythionaphthene, the 2- anils such as for exampleZ-(para-dimethylamino-)anils and 2-(para-hydroxy-anils-), 2- carboxylicacids, Z-oximes, Z-dihalides of these compounds, as well as4,6-dimethyl-5,7-dihalogenthionaphthenequinones obtainable from theabove Z-anils by saponification with mineral acids.

For making the indigoid dyestuffs suitable indigoid components are, forexample, hydroxythionaphthenes of the benzene, naphthalene, anthracene,and anthraquinone series; further indoxyls and isatines of the benzene,naphthalene and anthracene series; further phenols, naphthols,hydroxyanthracenes and hydroxycarbazoles, and finally also o-diketonesof the isocyclic series and. the products of thesehydroxythionaphthenes, phenols, hydroxycarbazoles and o-diketonessubstituted in the aryl-nuclei, i. e. in the benzene, naphthalene,anthracene and anthraquinone nuclei, by halogen groups, such as, forinstance, chlorine or bromine, alkyl-groups, alkoxy-groups, such as, forexample, methoxy or ethoxy-groups, wherein only one of several sub-'stituents, which may be similar or difierent, can be present. Thehydroxythionaphthenes and the indoxyls can be condensed as such with theindigoid components, or they can be used in the form of their reactive2-derivatives, for example as Z-anils EZ-(p-dimethylamino anils) or2-(hydroxyani1s)l, or as Z-carboxylic acids or as 2-oximes or as2-dihalides or as thionaphthenequinones. Also the isatines can becondensed as such, the oxygen atom of the isatines standing inB-position participating in the condensae tion, or they can be used inthe form of their reactive a-derivatives, such as, for example,isatine-u-halides. As is known, acenaphthenequine In SwitzerlandSeptember ones, phenanthrenequinones, and aceanthrenequinones belong forexample to the o-diketones of the isocyclic series.

The condensation of the 3-hydroxythionaphthenes of the above generalformula with the cited indigoid components takes place preferably byheating the mixture in a solvent or suspension which, if desired, canalso act as condensing agent. Such solvents or suspensions are, forinstance, water, alcohols, benzene, chlorobenzene, tetrachlorethane,glacial acetic acid and sulfuric acid.

The dyestuffs obtained of the general formula s V i wherein X representshalogen, Y alkyl and R the radical of an indigoid component, are pink,scarlet-red, red-violet, violet, and violet-blue to blue powders,dissolving in concentrated sulfuric acid to green to blue-greensolutions, and dyeing cotton from yellow, orange, red to violet vatspink, scarlet, red, red-violet, violet, and violet-blue to blue tints.

The new dyestuffs are particularly suitable for dyeing and printingvegetable and animal fibres, for instance, cotton, wool and silk, andare characterized by high coloring power, excellent purity, and verygood properties of fastness; they can be converted into theirleuco-ester salts by known methods, and after-halogenated with halogenor agents yielding halogen by known methods, for example by reactionwith chlorine or bromine in the presence of suspensions or solvents,such as, for example, water, nitrobenzene, trichlorobenzene,chlorobenzene or sulfuric acid.

The 3-hydroxythionaphthenes of the first mentioned general formula andtheir reactive 2-derivatives may be made by any known method; forexample, to make 4.6-dimethy15,7-dich1oro-3-hydroxythionaphthene thefollowing procedure may be adopted:-

From l-amino-2,4-dimethyl-G-benzenesulfonic acid there is made bydiazotization and reaction of the diazo-compound with cuprous chloridethe 1- chloro-2,4-dimethyl-6-benzene sulfonic acid, which by the actionof phosphorus pentachloride, is converted into thel-chloro-2,4-dimethyl-6- benzene-sulfochloride, which boils under 6 mm.pressure at 160-l61 C. and melts at til-62 C. This sulfochloride is nowreduced in usual manher, and the 1-chloro-2,4-dimethyl-G-thiophenol thusformed, which boils at 109-110 'C. under '7 mm. pressure, is condensedin alkaline solution with monochloracetic acid to the l-chloro-2,4-dimethyl-6-phenylthioglycollic acid melting at 117 C. The1-bromo-2,4-dimethyl-6phenylthioglycollic acid, obtainable in analogousmanner, melts at 114 C. By treating the l-chloro-2,4-dimethyl-6-phenylthioglycollic acid in, for example, chlorobenzenewith sulfuryl chloride there is obtained the 1,3-dichloro-2,4-dimethyl-G-phenylthioglycollic acid of melting point 155 C., whereas the1-bromo-3-chloro-2,4-dimethyl- 6-phenylthioglycollic acid of meltingpoint 161 C. is obtained in analogous manner from the 1-bromo-2,4-dimethyl-G-phenylthioglycollic acid. If the l-chloroor thel-bromo-2,4-dimethyl G-phenylthioglycollic acids are treated withbromine in similar manner, there is obtained the1chloro-3-bromo-2,4-dimethyl-6- phenylthioglycollic acid melting at 154C., or the 1,3-dibromo- 2,4-dimethyl-6-phenylthioglycollic acid ofmelting point 169 C. By treating these1,3-dihalogen-2,4-dimethyl-6-phenylthioglycollic acids with phosphorustrichloride and aluminium chloride, or with chlorosulfonic acid, thereare produced the corresponding hydroxythionaphthenes, such as, forexample, the 4,6-dimethyl-5,7-dichloro- 3-hydroxythionaphthene ofmelting point 224 C., the 4,6-dimethyl-5-chloro-7-bromo 3hydroxythionaphthene of melting point 231 C., the 4,6-dimethyl-5-bromo-7-chloro-3- hydroxythionaphthene of melting point 227C., and the 4,6-dimethyl-5,7-dibromo-3hydroxynaphthene melting above 270C.

From the hydroxythionaphthenes having the foregoing general formula thereactive 2-derivatives, for instance the 2-anils such as, for example,the 2(para-dimethylamino) anils, the 2- oximes, the 2-halides, are madein known manner by the action of nitroso-compounds, nitrous acid orhalogen; from the Z-anils by treatment with sulfuric acid the4,6-dialky1-5,7-dihalogenthionaphthenequinones are obtained. There isthus formed, for example, the 2-(para-dimethylamino-)anil of the4,6-dimethyl-5,7-dichloro-3- hydroxythionaphthene of melting point 272C. from 4,6-dimethyl-5,7-dichloro-3-hydroxythionaphthene by condensationwith para-nitrosodimethylaniline, which product, when treated at 40 C.with sulfuric acid of per cent. strength, is saponified to the4,6-dimethyl-5,7-dichlorothionaphthenequinone of melting point 153 C.

The following examples illustrate the invention, the parts being byweight:-

Emample 1 A mixture of 247 parts of4,6-dimethyl-5,7-dichloro-3-hydr-oxythionaphthene and 282 parts of2-(para-dimethylamino-)anil of 3-hydroxythionaphthene with 4000 parts ofalcohol is heated to boiling. When condensation is complete the dyestuffis filtered, washed and dried. The new dyestuff of the formula densedwith parts of S-hydroxythionaphthene.

Example 2 247 parts of 4,6-dimethyl-5,7-dichloro-3-hydroxythionaphtheneare dissolved in 2000 parts of chlorobenzene and the solution is mixedat 70 C. with a solution of 5,7-dibromisatin chloride, made from 305parts of 5,7-dibromisatin and 250 parts of phosphorus pentachloride inchlorobenzene in the known manner. After stirring for a short timecondensation is complete. Filtration, washing and drying follow, wherebythe dyestuff of the formula 31 1 31- is obtained in the form of a darkviolet powder soluble in concentrated sulfuric acid to a green solutionand dyeing cotton in a yellow vat fast pure blue-violet tints.

If in this example 216 parts of 5,7 dichlorisatin are substituted forthe 5,7 -dibromisatin a dyestuff of similar properties is obtained.

Dyestuffs dyeing similar tints are obtained when substituting in thisexample 291.5 parts of 4,6-dimethyl-5-chloro-7-bromo 3hydroxythionaphthene, or 291.5 parts of 4,6-dimethyl-5-bromo7chloro3-hydroxythionaphthene, or 336 parts of4,6-dimethyl-5,7-dibromo-3-hydroxythionaphthene for the 247 parts of4,6-dimethyl- 5,7-dichloro-3-hydroxythionaphthene.

If 247 parts of 4-methy1-5-chloro-7methoxyisatin are used instead of the5,7-dibromisatin there is obtained a dyestuff which dyes cotton pureblue very fast tints.

The same dyestuffs are obtained when using the equivalent quantities ofthe isatin-a-anilides instead of the isatine chlorides.

Example 3 A mixture of 247 parts of 4,6-dimethyl-5,7-dichloro-3-hydroxythionaphthene and 216 parts of 5,7-dichloroisatine isheated with 4000 parts of glacial acetic acid. When condensation iscomplete the dyestuff is filtered, washed and dried. The new dyestuff ofthe formula is a violet powder, soluble in concentrated sulfuric acid toa green solution, and dyes cotton from a yellow vat fast red-violettints.

If 305 parts of 5,7-dibromisatine, or 247 parts of4-methyl-5-chloro7-methoxyisatine are used instead of the5,7-dichloroisatine, there are obtained dyestuffs dyeing similar violettints.

Similar dyestuffs are further obtained when substituting in this example291.5 parts of 4,6- dimethyl -5-chloro-7-bromo-3-hydroxythionaphthene,or 291.5 parts of 4,6-dimethyl-5-bromo-7- chloro-3-hydroxythionaphthene,or 336 parts of 4,6- dimethyl -5,7- dibromo -3- hydroxythionaphthene forthe 4,6dimethyl-5,7-dichloro-3-hydroxythionaphthene.

furic acid to a green-blue solution, and dyes cotton from a yellow vatViolet tints.

Ewample 4 A mixture of 247. parts of 4,6-dimethyl-5,7-dich1oro-3-hydroxythionaphthene and 182 parts of acenaphthenequinone isheated with i000 parts of chlorobenzene. .When .condensation is completethe dyestuffis filtered, washed and dried. The new dyestuff of theformula is a scarlet powder, soluble in concentrated 'sul-' Example 5247 parts of 4-,6-dimethyl-5,7 dich1oro-3-hyr droxythionaphthene aredissolvedin4000 parts of glacial acetic acid, and this solution treatedin the cold with 320 parts of bromine. When formation of. the reactive4,6- dimethyl-5,7-dichloro-3-hydroxythionaphthene2 dibromide iscomplete, there are added 194 parts of othydroxyanthracene, and thewhole is stirred until the condensation is finished. The dyestuff isthen filtered, washed and;dried. The new dyestufi of the probableformula is a violet powder, soluble in concentrated Sui--3-hydroxythionaphthene,

4000 parts of concentrated sulfuric acid to which The same dyestufi isobtained if there are used for the condensation 379 parts ofZ-(para-dimethylamino-)anil of the 4.6-dimethyl-5,7-dichloro-3hydroxythionaphthene instead of the u- -dibromide of the4,6-dimethyl-5,7-dichloro-3-hydroxythionaphthene.

Similar dyestuffs are obtained when substituting in this example, on theone hand, equivalent proportions of other reactive phenols, preferably.naphthols, for the 4-chloro-a-naphthol, and, on

the other hand, equivalent proportions of 4,6-dimethyl-5-chloro-7 -bromo3 hydroxythionaphthene, or4,6-dimethyl-5-bromo-7-chloro-3-hydroxythionaphthene, or4,6-dimethyl-5,7-dibromo-3-hydroxythionaphthene, for the4,6-dimethyl-5,7-dichloro-3-hydroxythionaphthene or the ocdibromides ofthe corresponding 2-anils.

Example 6 421 parts of the dyestuff obtained by condensation of 247parts of 4,6-dimethyl-5,7-dichloro- 3-hydroxythionaphthene with 310parts of 2- (para-dimethylamino-)anil of the 4,7-dimethylare introducedinto 144 parts of bromine have be en added. After stirring for 10 hoursat ordinary temperature the mixture is heated to 30 within 10 hours andthen poured into water. The precipitated dyestuff is filtered, washedwith water and dried. The new dyestufi of the formula CH3 CH8 is a redpowder, soluble in concentrated sulfuric acid to a green solution, anddyes cotton from a yellow vat fast red-violet tints.

The following table gives further examples for, producing new valuableindigoid dyestuffs obtainable by the present invention from4,6-dimethyl-5,7-dichloro-3-hydroxythionaphthene, or4,6-dimethyl--chloro-7-bromo 3 hydroxythionaphthene, or4,6-dimethy1-5-bromo-7-chloro-3- hydroxythionaphthene, or4,6-dimethyl-5,7-dibromo-3-hydroxynaphthene Color in4,6-d1methyl-5,7-d1chloro-3-hydroxyth1onaph- Color of the Color of thetheme and: dyestufi C9101. of the vat dyed cotton iunc acid 12-(para-dimetl1-ylamino-) anil of the 5-ohloro-7- Red-violet Green-..Green-yellow Violet-red.

methyl-3-hydroxythionaphthene. 2 2-(para-dimethylamino-) anil of the 5-methyl-6- Red do Yellow Red. chloro-3-hydroxyth1onaphthene.

3 2-(para-dimethylamino-) anil of the 4-methy1-6- do do Brown-yellow--.Pink.

, chloro-3-hydroxythionaphthene. 4' 2-(para-dimethylamino-) anil of the6-chloro-3- do do Yellow Yellow-red.

hydroxythi'onaphthene. 5 2-(para-di1nethyla mino-) anil of the6-eth0xy-3- Brick red--. do- Orange Brick red.

hydroxythionaphthene. V 6 2-(para-dimethylamino-) anil of the5,7-dibromo- Red-violet do Yellow Red-violet.

3-hydroxythionaphthene. 7 2-(para-dimethylamino-) anil of the74,6-dimethdo do do Violet.

yl-7-ch1oro-3-hydroxythionaphthene. 8 2-gplara-diimeilzhylaminoq and ofthe 2,1-naphth- Bordeaux..--- do Orange Bordeaux.

lOlIl oxy 9 2-(para-dimethylamino,) anil of the 1,2-naphth- Mauv do doMauve.

. thioindoxyl. 10 2(para-dimethylamino'-) anil of the l-chloro-2,3-Blue. do do Blue-violet. naphththioindoxyl. 1 '11 ,Z-(tIJIeIa-dlimeEhyIaminW) anil of the 2,3-naphth- Violet do Orange-brown;Do. iomoxy. i 12 ?r(para-dime'thylamino-) anil oi the 4,7-dimeth- Red doYellow Red.

yl-3-hydroxythionaphthene. l3 2-(para-dimethylamino-) anil of the4,7(limethdo do do 1 Red-violet.

yl-5-chloro-3-hydroxythionaphthene.

OH; OH:

on; Q (25 CHI e V (25) Om \C 0 co o s 01 s \H O y o o Q Q 43 E6 Q 9 WhatI claim is:-- 1. Indigoid dyestuffs of the general formula wherein Xrepresents halogen, Y methyl and R the radical of an indigoid component,which products are scarlet, pink, red, red-violet, violet, andviolet-blue to blue powders, dissolving in concentrated sulfuric acid togreen, to blue-green solutions, and dyeing cotton from a yellow, orangeto red to violet vat scarlet, pink, red, red-violet, violet andviolet-blue to blue tints of good fastness.

2. Indigoid dyestuffs of the general formula 00 CO X M B, on, S 1%wherein X represents halogen and R1 an arylene radical, which productsare pink, red, and redviolet to violet powders, dissolving inconcentrated sulfuric acid to a green solution, and dyeing cotton from ayellow to orange vat pink, red, and redviolet to violet tints of goodfastness.

4. Indigoid dyestufis of the general formula wherein X representshalogen and R1 a phenylene radical, which products are pink, red andredviolet to violet powders, dissolving in concentrated sulfuric acid toa green solution, and dyeing cotton from a yellow to orange vat pink,red, and red-violet to violet tints of good fastness.

5. Indigoid dyestuffs of the general formula wherein R1 represents aphenylene radical, which products are pink, red, and red-violet toviolet powders, dissolving in concentrated sulfuric acid to a greensolution, and dyeingcotton from a yellow to orange vat pink, red, andred-violet to violet tints of good fastness.

6. The indigoid dyestuif of the formula on s S 1 CH;

which product represents a red-violet powder, dissolving in concentratedsulfuric acid to a green solution, and dyeing cotton from a yellow vatvery pure red-violet tints of good fastness.

'7. Indigoid dyestuffs of the general formula 5 wherein X representshalogen and R3 the radical arylene which products are violet,violet-blue to blue powders, dissolving in concentrated sulfuric acid toa green solution, and dyeing cotton from a yellow vat violet,violet-blue to blue tints of good fastness.

8. Indigoid dyestuffs of the general formula on H wherein X representshalogen and R3 an arylene radical, which products are violet,violet-blue to blue powders, dissolving in concentrated sulfuric acid toa green solution, and dyeing cotton from a yellow vat violet,violet-blue to blue tints of ood fastness.

9. Indigoid dyestuffs of the general formula wherein X representshalogen and R3 a phenylene radical, which products are violet,violet-blue to blue powders, dissolving in concentrated sulfuric acid toa green solution, and dyeing cotton from a yellow vat violet,violet-blue to blue tints of good fastness.

10. Indigoid dyestuffs of the general formula x 00 x C= on S/ NH whereinX represents halogen, which products are violet-blue powders, dissolvingin concentrated sulfuric acid to a green solution, and dyeing cottonfrom a yellow vat violet-blue tints of good fastness. 5

11. The indigoid dyestuff of the formula which product represents aviolet-blue powder, 7

dissolving in concentrated sulfuric acid to a green solution, and dyeingcotton from a yellow vat violet-blue tints of good fastness.

12. Indigoid dyestufis of the general formula 5 wherein X representshalogen and the carbon pair C1 0: belongs to a carbocyclic ring system15 which products are scarlet, orange, red to violet powders, dissolvingin concentrated sulfuric acid to green to blue solutions, and dyeingcotton from a yellow, orange, red to violet vat scarlet, orange red toviolet tints.

13. The indigoid dyestufi of the formula C=CO 0 on which productrepresents a scarlet powder, dissolving in concentrated sulfuric acid toa green solution, and dyeing cotton from a violet vat scar- 15 lettints.

ERNST STGCKLIN.

